CN114656343A - Method for preparing aldehyde and alcohol - Google Patents

Method for preparing aldehyde and alcohol Download PDF

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CN114656343A
CN114656343A CN202011535080.2A CN202011535080A CN114656343A CN 114656343 A CN114656343 A CN 114656343A CN 202011535080 A CN202011535080 A CN 202011535080A CN 114656343 A CN114656343 A CN 114656343A
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cobalt
catalyst
catalyst solution
reaction
olefin
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CN114656343B (en
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王海京
宗保宁
夏春谷
甄栋兴
丁晖殿
许传芝
郧栋
刘祺壬
罗一斌
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Lanzhou Institute of Chemical Physics LICP of CAS
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/786—Separation; Purification; Stabilisation; Use of additives by membrane separation process, e.g. pervaporation, perstraction, reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
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  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a process for preparing aldehydes and alcohols comprising: (1) adding a catalyst solution containing a cobalt-phosphine complex and a solvent into a reactor, contacting with C8-C30 olefin and synthesis gas, and reacting under the hydroformylation reaction condition; (2) separating the product obtained in the step (1), removing the product, removing part of the solvent and/or adding the catalyst to improve the mass concentration of the catalyst in a liquid phase to 1.1-300 times of the initial concentration, and improving the mass concentration of cobalt in a catalyst solution to 0.05% -3% to obtain a catalyst solution after reaction; (3) returning the reacted catalyst solution to the reactor, contacting with C8-C30 olefin and synthetic gas, performing hydroformylation reaction at 70-145 deg.c and 1-10MPa to separate alcohol and aldehyde. The method can greatly improve the reaction conversion rate and greatly improve the joint selectivity of aldehyde and alcohol at lower reaction temperature and pressure, thereby improving the yield of alcohol and aldehyde and simultaneously reducing the yield of low-value alkane.

Description

Method for preparing aldehyde and alcohol
Technical Field
The invention belongs to the field of preparation of oxygen-containing compounds, and particularly relates to a method for preparing aldehyde.
Background
Olefins are hydroformylated with carbon monoxide and hydrogen over a catalyst, the hydroformylation process comprising contacting under reaction conditions an ethylenically unsaturated compound with carbon monoxide and hydrogen in the presence of a catalyst to produce an alcohol, an aldehyde. Aldehydes produced by the hydroformylation process, also called oxo-aldehydes, have wide applicability as intermediates from which fatty alcohols can be obtained by addition of hydrogen; obtaining fatty amine through amination; fatty acid is obtained by oxidation, and the plasticizer can be produced by aldol condensation.
Catalysts used in hydroformylation reactions in commercial processes are typically cobalt (Co) based or rhodium (Rh) based catalysts.
CN102123978B discloses a process for hydroformylating an alpha-olefin to produce two or more aldehydes comprising a normal aldehyde and one or more isomeric aldehydes with a target molar ratio of the normal aldehyde to the one or more isomeric aldehydes in an alternative range of 3/1-60/1. The process uses a transition metal-ligand complex catalyst comprising a symmetric arene diphosphite ligand.
CN109776294A discloses a method for hydroformylation of olefins, comprising subjecting olefins and synthesis gas to a first stage reaction and a second stage hydroformylation reaction in the presence of a rhodium complex catalyst to produce aldehydes, wherein the temperature of the first stage reaction is at least 5 ℃ lower than the temperature of the second stage reaction. The invention adopts the sectional reaction, controls the temperature of the two-section reaction, and leads reactants to carry out the pre-reaction at lower temperature, thereby improving the performance of the catalyst and reducing the production cost.
CN108586219A discloses a method for preparing aldehyde by olefin hydroformylation, which comprises the following steps: the method comprises the following steps: continuously preparing aldehyde by hydroformylation of C2-C4 olefin, carbon monoxide and hydrogen under the action of a catalyst in a first reaction kettle at the temperature of 90 ℃ and the pressure of 2.5 MPa; step two: heating the mixture in a second reaction kettle at the temperature of between 70 and 80 ℃, and introducing inert gas into the second reaction kettle; step three: communicating the first reaction kettle with the second reaction kettle, and introducing the aldehyde prepared by the first reaction kettle into the second reaction kettle; step four: when the lead-in is carried out in the third step, the lead-in is carried out under the condition of constant pressure and unequal temperature, and the lead-in is carried out for the second time; the reaction process of the technology is complex, and the rhodium-phosphine complex catalyst is adopted, so that the price is high.
DE59704070D1 discloses a process for preparing alcohols having from 7 to 18 carbon atoms, which comprises hydroformylating the corresponding olefins with synthesis gas in the presence of an organic phase containing a cobalt catalyst at a pressure of 100-400 bar, followed by hydrogenation of the aldehydes thus obtained, wherein an aqueous solution of a cobalt salt is reacted with the synthesis gas in the presence of an organic solvent which is not miscible with water or is only sparingly miscible with water to form the cobalt catalyst, and the cobalt catalyst formed is extracted from the aqueous phase with an organic extractant which is not miscible with water or is only sparingly miscible with water to prepare the organic phase containing the cobalt catalyst. The reaction time is generally 10 hours or more.
Unless a noble metal Rh-based catalyst is used in the hydroformylation of olefins, if a cobalt (Co) -based catalyst is used, the reaction temperature is generally around 190 ℃ and the reaction pressure of the single cobalt (Co) -based catalyst is approximately 30 MPa.
The olefin hydroformylation reaction product contains alcohol, aldehyde and alkane, wherein the alkane has limited use and low value, the alcohol can be used in the fields of plasticizers, cosmetics, washing products, solvents, surfactants and the like, the use is wide, and the aldehyde can be converted into the alcohol through hydrogenation, so the aldehyde and the alcohol are high-value components. How to obtain higher yields of aldehydes and alcohols by hydroformylation is the current research direction in the field.
Disclosure of Invention
The invention provides a method for preparing aldehyde and alcohol by olefin hydroformylation, which can greatly improve the reaction conversion rate at lower reaction temperature and pressure, thereby improving the yield of aldehyde and alcohol and reducing the yield of low-value alkane.
The invention provides a method for preparing aldehyde and alcohol by olefin hydroformylation, which comprises the following steps:
(1) adding a catalyst solution containing a cobalt-phosphine complex and a solvent into a reactor, contacting with C8-C30 olefin and synthesis gas, and reacting under the hydroformylation reaction condition;
(2) separating the product obtained in the step (1), removing the product, removing part of the solvent and/or adding the catalyst to improve the mass concentration of the catalyst in a liquid phase to 1.1-300 times of the initial concentration, and improving the mass concentration of cobalt in a catalyst solution to 0.05% -3% to obtain a catalyst solution after reaction;
(3) returning the reacted catalyst solution to the reactor, contacting with C8-C30 olefin and synthetic gas, performing hydroformylation reaction at 70-145 deg.c and 1-10MPa to separate alcohol and aldehyde.
According to the method of the present invention, the cobalt-phosphine catalyst solution of step (1) may be prepared as follows: dissolving cobalt-containing raw material and phosphine ligand in solventIn the middle, CO and H are charged2The gas is brought to a pressure of 1-6MPa, preferably 2-4MPa, and the reaction is carried out at 70-180 ℃, preferably 120-160 ℃ for 0.5-18h, preferably 2-12h, to obtain the cobalt-phosphine catalyst solution.
The cobalt-containing material may be cobalt salt or cobalt oxide, wherein the cobalt salt may be inorganic cobalt or organic cobalt, such as one or more selected from cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt levulinate, cobalt formate, cobalt octacarbonyl cobaltate and cobalt naphthenate.
The phosphine ligand can be one or more of phosphite ester, triphenylphosphine, trialkyl phosphine, di- (triphenylphosphine), alkyl phenyl phosphine and the like, and triphenylphosphine or tributylphosphine is preferred.
Wherein the mass ratio of cobalt to phosphorus of the cobalt-containing raw material to the phosphine ligand can be 1 (0.1-3), preferably 1 (0.2-2), and more preferably 1 (0.3-1).
Wherein the solvent can be various solvents known in the art to be suitable for hydroformylation reaction, such as alkene, alkane, alcohol, etc., and the solvent can contain product or raw material, preferably various normal and isomeric alcohols containing C1-C20, such as isononyl alcohol, isodecyl alcohol, etc.
Wherein the mass concentration of cobalt in the catalyst solution of the step (1) is 0.01-0.4%, preferably 0.05-0.35%, more preferably 0.08-0.30%. In experiments, the inventor of the present application found that the solubility of the cobalt-phosphine catalyst in the above solvent is not high, and usually the mass concentration of cobalt reaches at most 0.3-0.4%, and the cobalt-phosphine catalyst is precipitated from the solvent after exceeding the mass concentration.
The olefin is a C8-C30 olefin, preferably a C8-C12 olefin, more preferably a C8 olefin. The C8 olefin is preferably a multibranched olefin, for example, 2,4, 4-trimethyl-1-pentene, 2,4, 4-trimethyl-2-pentene. The olefins may be derived from Fischer-Tropsch products, or may be highly branched or less branched olefins derived from the dimerisation (folding) of mixed four carbon olefins.
The synthesis gas refers to a mixed gas of carbon monoxide and hydrogen, wherein the molar ratio of the carbon monoxide to the hydrogen is 4:1-1:4, preferably 3:1-1:3, and more preferably 2:1-1: 2.
The molar ratio of the C8-C30 olefin to the synthesis gas is 1: (2-12), preferably 1: (3-9), more preferably 1: (4-6).
According to the process of the present invention, the mass ratio of the catalyst solution to the olefin in step (1) can be varied over a wide range, but too high a mass ratio of the catalyst solution to the olefin increases the energy consumption and the operating cost of the apparatus, and decreases the utility of the equipment. Therefore, the catalyst solution to olefin mass ratio is (0.1 to 4): 1, preferably (0.3-3.5): 1, more preferably (0.6-3): 1.
the reactor in the step (1) can adopt an autoclave or a tubular reactor. The hydroformylation reaction temperature can be 60-220 ℃, preferably 100-180 ℃, more preferably 120-160 ℃, and the pressure is 1-10MPa, preferably 3-9MPa, more preferably 5-8 MPa; the reaction time may be 1 to 40 hours, preferably 4 to 20 hours, most preferably 5 to 8 hours.
According to the method of the invention, the product of step (1) is separated in step (2), and unreacted olefin and synthesis gas can be removed by gas-liquid separation or flash evaporation, and the like, and then the product alkane, alcohol and aldehyde are distilled out by means of atmospheric distillation, reduced pressure distillation, thin film evaporation and the like, and then partial solvent is distilled out and/or the product is distilled out, and then the catalyst concentration is increased by increasing the catalyst, so that the catalyst concentration is increased to 1.1-300 times, preferably 1.5-10 times, more preferably 2-5 times of the initial concentration, and the mass concentration of cobalt in the catalyst solution is 0.05-3%, preferably 0.1-2%, more preferably 0.2-1.2%, and most preferably 0.2-0.8%.
The inventor of the present application has unexpectedly found that after the hydroformylation reaction of step (1) is completed, the concentration of the cobalt-phosphine catalyst in the reaction system can be greatly increased, and the cobalt-phosphine catalyst will not be precipitated even if part of the solvent is distilled off after the product is distilled off and/or the catalyst is added, so that the cobalt content in the catalyst solution is increased to 1.1-300 times of the initial concentration. If the catalyst is not precipitated in step (1), a high-concentration catalyst solution cannot be obtained. According to the common knowledge of the skilled person, the prior operation process needs to keep the catalyst at a basically constant concentration, so that the solvent is not distilled off additionally when the product is distilled off; even if the solvent is the same as the product, e.g., isononanol, the initial amount of solvent is retained upon distilling off the product.
According to the method of the invention, the catalyst solution after the reaction in the step (3) is returned to the reactor and contacted with C8-C30 olefin and synthesis gas to carry out hydroformylation reaction. Wherein the reaction temperature may be 70-145 ℃, preferably 100-140 ℃, more preferably 110-140 ℃, most preferably 120-135 ℃; the pressure is 1-10MPa, preferably 3-9MPa, more preferably 6-8 MPa; the reaction time is 1 to 40 hours, preferably 5 to 20 hours, more preferably 6 to 10 hours.
Preferably, after the catalyst solution and the synthesis gas are introduced into the reactor after the reaction, the pretreatment is carried out for 1 to 2 hours, and then C8 to C30 olefins are introduced for the hydroformylation reaction.
According to the common knowledge of the people in the art, aldehydes, alcohols and alkanes can be obtained from the products of the hydroformylation of olefins, the reaction conversion rate is generally higher at higher temperature (for example, about 190-210 ℃), but the alkane selectivity is higher, and the aldehyde selectivity is very low, so that the total yield of the alcohols and the aldehydes is lower; when the reaction temperature is low (e.g., 100 ℃ C. and 150 ℃ C.), the conversion rate is greatly reduced, and thus the reaction is not usually carried out at such a low temperature.
The present inventors have unexpectedly found that the reactivity of the catalyst solution is improved after the reaction of step (1), and the selectivity of the alcohol and aldehyde is significantly improved even at a relatively low reaction temperature (e.g., 100 ℃ C. and 150 ℃ C.) when the reaction of step (3) is carried out by adding the catalyst solution after the reaction into the reactor.
The inventor of the present application further finds that, when the hydroformylation reaction is carried out by using a high-concentration catalyst, the reaction conversion rate can be greatly improved even at a relatively low reaction temperature, and the selectivity of alcohol and aldehyde can be obviously improved due to the above reasons, so that the yield of alcohol and aldehyde in the product can be remarkably increased, and the yield of alkane can be greatly reduced.
The method adopts a non-noble metal catalyst, has lower reaction temperature than the conventional cobalt-based hydroformylation catalyst, can perform hydroformylation reaction on the olefin with high branching degree which is difficult to react, reduces the reaction energy consumption, greatly improves the economical efficiency of the process, and has good industrial application prospect.
Detailed Description
The invention is further illustrated below by way of examples, without being limited thereto.
The olefin feed in the examples was a commercially available C8 olefin having the composition: 75.1% of 2,4, 4-trimethyl-1-pentene, 21.2% of 2,4, 4-trimethyl-2-pentene and the balance multi-branched olefins.
In the following examples, the product composition was determined by chromatography.
Catalyst preparation example 1
Dissolving cobalt naphthenate and triphenylphosphine in isononyl alcohol to ensure that the cobalt content in the solution is 0.23 percent and the phosphorus content is 0.16 percent, completely replacing air by using synthesis gas H2/CO (2:1), filling CO and H2 gas until the pressure is 1.5MPa, and reacting for 10 hours at 130 ℃ under the stirring of 400 r/min to obtain a cobalt-phosphine catalyst solution A1. The catalyst composition is shown in table 1.
Catalyst preparation example 2
Dissolving cobalt naphthenate and triphenylphosphine in isononyl alcohol to ensure that cobalt accounts for 0.20% and phosphorus accounts for 0.14% in the solution, completely replacing air with synthesis gas H2/CO (2:1), filling CO and H2 gas until the pressure is 1.5MPa, and reacting for 10 hours at 130 ℃ under the stirring of 400 revolutions per minute to obtain a cobalt-phosphine catalyst solution A2. The catalyst composition is shown in table 1.
Catalyst preparation example 3
Dissolving cobalt naphthenate and triphenylphosphine in isononyl alcohol to ensure that the cobalt content in the solution is 0.32 percent and the phosphorus content is 0.17 percent, completely replacing air by using synthesis gas H2/CO (2:1), filling CO and H2 gas until the pressure is 1.5MPa, and reacting for 10 hours at 130 ℃ under the stirring of 400 r/min to obtain a cobalt-phosphine catalyst solution A3. The catalyst composition is shown in table 1.
Catalyst preparation example 4
Dissolving cobalt naphthenate and triphenylphosphine in isononyl alcohol to ensure that the cobalt content in the solution is 0.14 percent and the phosphorus content is 0.10 percent, completely replacing air by using synthesis gas H2/CO (2:1), filling CO and H2 gas until the pressure is 1.5MPa, and reacting for 10 hours at 130 ℃ under the stirring of 400 r/min to obtain a cobalt-phosphine catalyst solution A4. The catalyst composition is shown in Table 1.
Catalyst comparative example 1
Adding cobalt naphthenate and triphenylphosphine into isononyl alcohol to ensure that the cobalt content in the solution is 0.40 percent and the phosphorus content is 0.30 percent, completely replacing air by using synthesis gas H2/CO (2:1), filling CO and H2 gas until the pressure is 1.5MPa, and reacting for 10 hours at 130 ℃ under the stirring of 400 r/min to obtain a cobalt-phosphine catalyst solution B1. The catalyst precipitation phenomenon appears in the catalyst solution, which shows that the cobalt-phosphine catalyst has small solubility and low concentration in the isononyl alcohol solvent. The catalyst composition is shown in table 1.
Example 1
Adding a 1190 g catalyst solution into an autoclave, wherein the cobalt content and the phosphorus content in the catalyst solution are 0.23% and 0.16% respectively, pretreating for 1 hour under the conditions of 110 ℃, 8MPa of pressure, 500 rpm of stirring speed and synthesis gas (H2/CO2:1), then adding 100g of C8 olefin, reacting for 8 hours under the conditions of 140 ℃, 8MPa of pressure, 500 rpm of stirring speed and synthesis gas (H2/CO2:1), and carrying out gas-liquid separation on a reaction crude product, wherein a liquid phase enters a thin film evaporator, the pressure of the thin film evaporator is 4mmHg, the heating surface temperature is 90 ℃, after the product and part of solvent are evaporated by the thin film evaporator, the cobalt content and the phosphorus content in the residual catalyst solution are 0.60% and 0.44%, the catalyst is not precipitated, and the residual catalyst solution is used as a catalyst solution for the second step of reaction for later use.
The second step of reaction: 45g of the above-mentioned catalyst solution was charged into an autoclave, pretreated for 1 hour under the conditions of 110 ℃ under a pressure of 8MPa, a stirring rate of 500 rpm and a synthetic gas (H2/CO2:1), 21g of C8 olefin was added, and the reaction was carried out for 8 hours under the conditions of 130 ℃ under a pressure of 8MPa, whereby the conversion of C8 olefin was 92.3%, and the product composition was as shown in Table 2.
Example 2
Adding a catalyst solution A1190 g into an autoclave, pretreating for 1 hour under the conditions of 120 ℃, 8MPa of pressure, 500 r/min of stirring speed and synthesis gas (H2/CO2:1), then adding 115g of C8 olefin, reacting for 8 hours under the conditions of 120 ℃, 8MPa of pressure, 500 r/min of stirring speed and synthesis gas (H2/CO2:1), wherein a reaction crude product is subjected to gas-liquid separation, a liquid phase enters a thin film evaporator, the pressure of the thin film evaporator is 3mmHg, the heating surface temperature is 75 ℃, after the product and part of solvent are evaporated by the thin film evaporator, the cobalt content in the residual catalyst solution is 0.64 percent, the phosphorus content is 0.46 percent, the catalyst is not separated out, and the residual catalyst solution is used as a second-step reaction catalyst solution for later use.
The second step of reaction: 44g of the above-mentioned catalyst solution was charged into an autoclave, pretreated for 1 hour at 120 ℃ under a pressure of 8MPa and a stirring rate of 500 rpm under a condition of synthesis gas (H2/CO2:1), and then 21g of C8 olefin was added, reacted for 8 hours at 120 ℃ under a pressure of 8MPa and a stirring rate of 500 rpm, at a conversion of C8 olefin of 97.8%, and the composition of the product was as shown in Table 2.
Example 3
Adding a catalyst solution A1190 g into an autoclave, pretreating for 1 hour under the conditions of 140 ℃, 8MPa of pressure, 500 r/min of stirring speed and synthesis gas (H2/CO2:1), then adding 90g of C8 olefin, reacting for 8 hours under the conditions of 180 ℃, 8MPa of pressure, 500 r/min of stirring speed and synthesis gas (H2/CO2:1), and carrying out gas-liquid separation on a reaction crude product, wherein a liquid phase enters a thin film evaporator, the pressure of the thin film evaporator is 0.6mmHg, the heating surface temperature is 60 ℃, after the thin film evaporator evaporates the crude product and part of solvent, the cobalt content in the residual catalyst solution is 0.51 percent, the phosphorus content is 0.37 percent, the catalyst is not precipitated, and the residual catalyst solution is used as the catalyst solution for the second step of reaction for later use.
The second step of reaction: 42g of the above-mentioned catalyst solution was charged into an autoclave, pretreated for 1 hour under 140 ℃ and 8MPa of pressure, a stirring rate of 500 rpm, and a synthetic gas (H2/CO2:1), 30g of C8 olefin was added, and reacted for 8 hours under 140 ℃ and 8MPa of pressure, whereby the conversion of C8 olefin was 99.8%, and the composition of the product was as shown in Table 2.
Example 4
Adding a catalyst solution A2130 g into an autoclave, pretreating for 1 hour under the conditions of 130 ℃, 8MPa of pressure, 500 r/min of stirring speed and synthesis gas (H2/CO2:1), then adding 60g of C8 olefin, reacting for 8 hours under the conditions of 180 ℃, 8MPa of pressure, 500 r/min of stirring speed and synthesis gas (H2/CO2:1), and carrying out gas-liquid separation on a reaction crude product, wherein a liquid phase enters a thin film evaporator, the pressure of the thin film evaporator is 0.7mmHg, the heating surface temperature is 70 ℃, after the thin film evaporator evaporates the crude product and part of solvent, the cobalt content in the residual catalyst solution is 0.40%, the phosphorus content is 0.30%, the catalyst is not precipitated, and the residual catalyst solution is used as a second-step reaction catalyst solution for later use.
The second step of reaction: 42g of the above-mentioned catalyst solution was charged into an autoclave, pretreated for 1 hour under 130 ℃ and 8MPa of pressure, a stirring rate of 500 rpm, and a synthetic gas (H2/CO2:1), 30g of C8 olefin was added, and reacted for 4 hours under 130 ℃ and 8MPa of pressure, whereby the conversion of C8 olefin was 85.9%, and the composition of the product was as shown in Table 2.
Comparative example 1
Adding a catalyst solution A390 g into an autoclave, pretreating for 1 hour under the conditions of 130 ℃, 8MPa of pressure, 500 r/min of stirring speed and synthesis gas (H2/CO2:1), then adding 100g of C8 olefin, reacting for 9 hours under the conditions of 130 ℃, 8MPa of pressure, 500 r/min of stirring speed and synthesis gas (H2/CO2:1), and carrying out gas-liquid separation on a reaction crude product, wherein a liquid phase enters a thin film evaporator, the pressure of the thin film evaporator is 0.9mmHg, the heating surface temperature is 60 ℃, after partial crude product and/or solvent is evaporated by the thin film evaporator, the cobalt content and the phosphorus content in the residual catalyst solution are 0.17 percent and 0.10 percent respectively, the catalyst is not separated out, and the residual catalyst solution is used as a second-step reaction catalyst solution for standby.
The second step of reaction: 35g of the spare catalyst solution is added into an autoclave, the cobalt content and the phosphorus content in the catalyst solution are respectively 0.17 percent and 0.10 percent, 30g of C8 olefin is added after pretreatment is carried out for 1 hour under the conditions of 130 ℃, 8MPa of pressure and 500 r/min of stirring speed and synthesis gas (H2/CO2:1), and the conversion rate of the C8 olefin is 72.6 percent after reaction is carried out for 4 hours under the conditions of 130 ℃, 8MPa of pressure and 500 r/min of stirring speed. The product composition is shown in Table 2.
Comparative example 2
One-step reaction: a446 g catalyst solution with 0.14% cobalt and 0.10% phosphorus was added to the autoclave, and after pretreatment for 1 hour at 120 deg.C under 8MPa with 500 rpm stirring speed and H2/CO2:1, 21g of C8 olefin was added and the reaction was carried out for 8 hours at 180 deg.C under 8MPa with 500 rpm stirring speed, with 81.9% conversion of C8 olefin, the composition of the product being shown in Table 2.
Example 2 the second step reaction is compared with the first step reaction of comparative example 2, it can be known that the second step reaction of example 2 can improve the catalyst concentration, the catalyst does not precipitate; the reaction temperature can be reduced, the selectivity of 2, 4-trimethylpentane is obviously reduced, the joint selectivity of isononanal and isononanol is greatly increased, the second step of the example 2 can obtain high conversion rate, and the economic benefit of the device is obviously improved.
Comparative example 3
One-step reaction: the catalyst solution A335 g was charged into an autoclave, the cobalt content in the solution was 0.32%, the phosphorus content was 0.17%, 30g of C8 olefin was added after 1 hour of pretreatment under the conditions of 130 ℃, 8MPa, stirring speed 500 rpm, and synthesis gas (H2/CO2:1), and the reaction was carried out for 4 hours under the conditions of 130 ℃, 8MPa, 500 rpm, and stirring, the conversion of C8 olefin was 49.6%, and the composition of the product was shown in Table 2.
Comparative example 3 illustrates that: the reaction in one step with a higher catalyst concentration was carried out at the same lower reaction temperature as in the second reaction in example 4, and the reaction conversion was low.
TABLE 1 compositions of catalyst preparation examples and comparative examples
Figure BDA0002853090700000131
TABLE 2
Figure BDA0002853090700000132

Claims (15)

1. A method of making an alcohol and an aldehyde comprising:
(1) adding a catalyst solution containing a cobalt-phosphine complex and a solvent into a reactor, contacting with C8-C30 olefin and synthesis gas, and reacting under the hydroformylation reaction condition;
(2) separating the product obtained in the step (1), removing the product, removing part of the solvent and/or adding the catalyst to improve the mass concentration of the catalyst in a liquid phase to 1.1-300 times of the initial concentration, and improving the mass concentration of cobalt in a catalyst solution to 0.05% -3% to obtain a catalyst solution after reaction;
(3) returning the reacted catalyst solution to the reactor, contacting with C8-C30 olefin and synthetic gas, performing hydroformylation reaction at 70-145 ℃ and 1-10MPa, and separating the product aldehyde and alcohol.
2. The process of claim 1 wherein the cobalt-phosphine catalyst solution of step (1) is prepared by the following process: dissolving cobalt-containing raw material and phosphine ligand in solvent, charging CO and H2The gas is brought to a pressure of 1-6MPa, preferably 2-4MPa, and the reaction is carried out at 70-180 ℃, preferably 120-160 ℃ for 0.5-18h, preferably 2-12h, to obtain the cobalt-phosphine catalyst solution.
3. The method according to claim 2, wherein the cobalt-containing raw material is one or more selected from the group consisting of cobalt oxide, cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt levulinate, cobalt formate, cobaltocene octacarbonyl and cobalt naphthenate.
4. The process according to claim 2, wherein the phosphine ligand is selected from one or more of phosphite, triphenylphosphine, trialkylphosphine, di- (triphenylphosphine), alkylphenylphosphines.
5. A process according to claim 2, wherein the mass ratio of cobalt to phosphorus of the cobalt-containing feedstock to phosphine ligand is from 1 (0.1 to 3), preferably from 1 (0.2 to 2), more preferably from 1 (0.3 to 1).
6. The process of claim 2 wherein the solvent comprises normal and isomeric alcohols having the formula C1 to C20.
7. The process according to claim 1, wherein the cobalt concentration in the catalyst solution of step (1) is from 0.01% to 0.4%, preferably from 0.05% to 0.35%, more preferably from 0.08% to 0.30% by mass.
8. The process according to claim 1, wherein the synthesis gas has a molar ratio of carbon monoxide to hydrogen of from 4:1 to 1:4, preferably from 3:1 to 1:3, more preferably from 2:1 to 1: 2.
9. The process of claim 1 wherein the molar ratio of C8-C30 olefin to syngas is from 1: (2-12), preferably 1: (3-9), more preferably 1: (4-6).
10. The process according to claim 1, wherein the mass ratio of catalyst solution to olefin is (0.1-4): 1, preferably (0.3-3.5): 1, more preferably (0.6-3): 1.
11. the method according to claim 1, wherein the reactor in step (1) is an autoclave or a tubular reactor.
12. The process according to claim 1, wherein the hydroformylation reaction temperature of step (1) is 60 ℃ to 220 ℃, preferably 100 ℃ to 180 ℃, more preferably 120 ℃ to 160 ℃; a pressure of from 1MPa to 10MPa, preferably from 3MPa to 9MPa, more preferably from 5MPa to 8 MPa; the reaction time is from 1 to 40 hours, preferably from 4 to 20 hours, most preferably from 5 to 8 hours.
13. The process according to claim 1, wherein in the step (2), the product of the step (1) is separated, and the unreacted olefin and the synthesis gas are removed by gas-liquid separation or flash evaporation, and then the alkane, the alcohol and the aldehyde are distilled off by atmospheric distillation, vacuum distillation or thin film evaporation, respectively.
14. The process according to claim 1, wherein in step (2), the catalyst concentration is increased by distilling off the solvent and/or increasing the catalyst to 1.5 to 10 times, preferably 2 to 5 times the initial concentration, and the mass concentration of cobalt in the catalyst solution is 0.1 to 2%, preferably 0.2 to 1.2%, more preferably 0.2 to 0.8%.
15. The process according to claim 1, wherein in step (3), the reaction temperature is 100-140 ℃, preferably 110-140 ℃, more preferably 120-135 ℃; the pressure is 1MPa to 10MPa, preferably 3MPa to 9MPa, more preferably 6MPa to 8 MPa; the reaction time is 1 to 40 hours, preferably 5 to 20 hours.
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